The evolution of hydrochemical compositions influenced by long-period interactions between groundwater and the geo-environment is a fundamental issue for exploring groundwater quality and vulnerability. This study systematically investigated the hydrochemical processes and anthropogenic interference occurring in the river basin by bivariate plots, Gibbs diagrams, saturation index, and the major ions ratios. Apparent changes in groundwater hydrochemistry have been observed in the study area, illustrating the origins of major ions are affected by various internal and external factors. Results highlighted that TDS varied from freshwater to brackish water, ranging between 187.90 and 2294.81 mg/L. Ca²⁺ and HCO ⁻₃ are the dominant ions in the studied samples. The results gained by Gibbs diagrams, bivariate plots, saturation index, and the major ions ratios demonstrated that minerals dissolution/precipitation, cation exchange, and human inputs play crucial roles in the unconfined aquifers. Moreover, the overuse of nitrogen fertilizer, livestock manure, and industrial/domestic sewage led to nitrate and nitrite contamination and brought significant challenges to the surrounding hydrogeo-environment. The present study could make an unambiguous identification of natural processes and anthropogenic interventions influencing groundwater hydrochemistry’s long-period evolution and create a preliminary strategy for groundwater resources management.